Naphtholactam dyestuffs

ABSTRACT

A naphtholactam dyestuff of the general formula (1) ##STR1## in which R represents C 1  -C 5  -alkyl, C 1  -C 5  -alkenyl, C 6  -C 9  -cycloalkyl, C 6  -C 9  -aralkyl, aryl or, preferably, hydrogen, X represents --COOH, --COO.sup.⊖ cation.sup.⊕, a modified carboxyl group, the radical --SO 2  --T or a heterocyclic radical, T denoting alkyl, alkenyl or, preferably, aryl, M represents hydrogen or a cation, Y represents a free or modified carboxyl group, Z is C 1  -C 4  -alkyl, C 1  -C 4  -alkoxy, Cl, Br, NO 2 , phenyl sulphonyl C 1  -C 4  -alkyl-S, C 1  -C 4  -alkyl sulphonyl, cyano, CONH 2 , CONH-C 1  -C 4  -alkyl, and CON(C 1  -C 4  -alkyl) 2 , n represents 0, 1 or 2, A represents a heterocyclic radical or --CN and B and C can carry further non-ionic substituents. 
     The new dyestuffs give brilliant yellow and red shades on polyester and polyamide fibers.

This is a continuation of application Ser. No. 793,564 filed on May 4,1977 now abandoned.

The invention relates to naphtholactam dyestuffs of the general formula(I) ##STR2## in which R represents alkyl, alkenyl, cycloalkyl, aralkyl,aryl or, preferably, hydrogen, X represents --COOH, --COO⁶³ cation⊕, amodified carboxyl group, the radical --SO₂ --T or a heterocyclicradical, T denoting alkyl, alkenyl or, preferably, aryl, M representshydrogen or a cation, Y represents a free or modified carboxyl group, Zrepresents a non-ionic substituent, n represents 0, 1 or 2 and Arepresents a heterocyclic radical or --CN and B and C can carry furthernon-ionic substituents.

The new dyestuffs of the formula (I) can be manufactured by variousprocesses.

A particularly advantageous process consists in subjecting anaphtholactam compound of the formula (II) ##STR3## to a condensationreaction, in the presence of an acid condensing agent, preferablyphosphorus oxychloride, with a compound of the formula

    X--CH.sub.2 --A                                            (III)

which contains an active methylene group, and optionally subsequentlysulphonating, brominating, chlorinating, nitrating and/or saponifyingthe resulting condensation product; in formulae (II) and (III) R, X, Y,Z, A, B, C and n have the meaning indicated above.

Another of these processes is characterised in that a compound of theformula ##STR4## in which W represents a C₁ -C₄ -alkyl radical,preferably methyl or ehtyl, An represents an anion, and R, Z, Y, B, Cand n have the meaning indicated above, is subjected to a condensationreaction with a compound of the formula

    X--CH.sub.2 --A                                            (V)

in which X and A have the same meaning as above, W--SH and H--An beingsplit off, and, if desired, the resulting condensation product issulphonated, brominated, chlorinated, nitrated and/or saponified.

Dyestuffs of the formula (I) in which X is --CO--OR₁, --CO--Q, --SO₂--T, a heterocyclic structure or, preferably, --CN, in which R₁ denotesoptionally substituted alkenyl, cycloalkyl, aralkyl, aryl or,preferably, alkyl, T has the same meaning as above and Q is the radicalof an amine of the formula Q--H, Y represents --CN, --COCl, --CO--Q' or,preferably, --CO--OR₁ ', in which Q' is the radical of an amine H--Q'and R₁ ' is optionally substituted alkyl, alkenyl, cycloalkyl, aralkylor aryl or a heterocyclic radical, Z represents bromine, chlorine orhydrogen and A and R have the same meaning as above, are preferred.

The radical A is preferably a heterocyclic structure of the formula##STR5## in which Z' represents the members necessary to complete aheterocyclic 5-membered or 6-membered ring, which can also contain fusedaromatic rings, and in which the rings can contain non-ionicsubstituents.

Particularly preferred dyestuffs are derived from the reactivederivatives o benzimidazole, benzoxazole, benzthiazole, pyridine,quinoline, phenanthridine, indolenine, thiadiazole, triazole, pyrimidineand isoquinoline.

X preferably denotes cyano and if it represents a heterocyclic structurealso denotes, for example, the group of the formula ##STR6## in which Z'is the same as above.

In the carboxamide groups --CO--Q and --CO--Q', Q and Q', whichrepresent the radicals of the amines of QH and Q'H, independently of oneanother denote methylamino, ethylamino,dimethylamino, diethylamino,dipropylamino, di-n-butylamino, N-methyl-N-butylamino, N-(2-hydroxy-,2-chloro-, 2-methoxy-, 2-bromo- or 2-cyano-ethyl)-amino,N,N-di-(2-hydroxy-, 2-chloro-, 2-methoxy- or 2-cyanoethyl)-amino,N-2-cyanoethyl-N-ethylamino-, N-2-cyanoethyl-N-2-hydroxyethylamino,N-2-lower alkoxy (for example C₁ -C₄ -alkoxy)-N-lower alkyl (for exampleC₁ -C₄ -alkyl-, especially methyl)-amino,N-methoxyethyl-N-cyanoethylamino, N-methyl-N-ethylamino,N-2-methylthioethylamino, N-2-methylsulphonylethylamino,γ-methoxypropylamino, γ-cyanopropylamino, γ-carboxypropylamino,γ-sulphopropylamino, N-hydroxyethyl-N-cyclohexylamino,3-hydroxy-1,1-dimethyl-propylamino, benzylamino, o-, m- orp-nitrobenzylamino, o-, m- or p-methylbenzylamino, o-, m- orp-methoxybenzylamino, phenylethylamino, cyclohexylamino,methylcyclohexylamino, 2,2,5-trimethylcyclohexylamino,dicyclohexylamino, tetramethylenesulphonyl-3-amino, N-pyrrolidinyl,N-piperidinyl, N-methylpiperidinyl, N-morphonlinyl,N-4-sulphopiperidinyl (N-thiomorpholinyl), ##STR7## (for examplemethyl-piperazinyl), N-(N'- lower alkylcarbonyl (for exampleacetyl)-piperazinyl N-(N'-hydroxyethyl)-piperazinyl, phenylamino, o-, p-or m-chloro-phenylamino, 3,6-dichlorophenylamino, o-, m- orp-bromophenylamino, o- or p-fluorophenylamino,m-trifluoromethylphenylamino, m- or p-nitrophenylamino, o-, m- orp-methylphenylamino, o-, m-or p-lower alkoxyphenylamino, such as o-, m-or p-methoxyphenylamino, m- or p-carboxyphenylamino, m- orp-carboxamidophenylamino, m- or p-acetamidophenylamino, p- orm-aminosulphonylphenylamino,m-bis-(hydroxyethylamino)-sulphonylphenylamino,methylsulphonyl-phenylamino, p-(2-hydroxyethyl)-sulphonylphenylamino,N-cyclohexyl-N-phenylamino, N-methyl-N-phenylamino,N-phenyl-N-2-hydroxyethylamino, N-phenol-N-2-cyanoethyl-amino,N-p-chlorophenyl-N-2-hydroxyethylamino, p-phenoxyphenylamino,p-(p'-chlorophenoxy)-phenylamino, p'-methylphenoxyphenylamino,m-chloro-o-phenoxy phenylamino, p-benzylphenylamino andp-acetamidophenylamino and p-propionylamidophenylamino, amino radicalsof the formula ##STR8## in which Z has the same meaning as above, suchas, for example, thiazolyl-2-amino, benzthiazolyl-2-amino,benzoxazolyl-2-amino, 1,3,4-triazolyl-2-amino,1-thia-3,4-diazolyl-2-amino and benzimidazolyl-2-amino and theirmethoxy, ethoxy, phenyl, chlorine, bromine, methyl, ethyl, carbomethoxyand carboethoxy derivatives, α- and β-tetrahydrofurfurylamino,2-furfurylamino, N-α- and -β-tetrahydrofurfuryl-N-methylamino,thiophenyl-2-amino and pyridyl-3-amino, and the amino radicals derivedfrom sulphanilic acid and taurine.

Preferably, the amines HQ and HQ' are so chosen that the radicals Q andQ' represent the groups of the formulae NHR₁ ' and NR₁ 'R₂ ', in whichR₁ ' and R₂ ' are optionally substituted aralkyl radicals and, if R₁ 'is an optionally substituted lower alkyl radical, R₂ ' can also be anoptionally substituted aryl radical and, if R₁ ' is a hydrogen atom, R₂' can be an optionally substituted alkyl radical, an optionallysubstituted aralkyl radical or an optionally substituted aryl radical.

Radicals R are, in addition to hydrogen, in particular alkyl with 1 to 8carbon atoms, hydroxyalkyl with 2 or 3 carbon atoms, alkoxyalkyl with 3to 8 carbon atoms, β-chloroethyl, β-cyanoethyl, alkoxycarbonylethyl with1 to 4 carbon atoms in the alkoxy, carbamoylethyl, N-monosubstituted orN,N-disubstituted alkylcarbamoylethyl with 1 to 4 carbon atoms in thealkyl, cyclohexyl, benzyl, phenylethyl or phenyl and also alkenyl.Aliphatic groups and also benzyl and phenylethyl are preferred.

Examples which may be mentioned individually are: propyl, butyl, hexyl,β-ethylhexyl, β-hydroxyethyl or β-hydroxypropyl, methoxyethyl,ethoxyethyl, methoxypropyl, ethoxypropyl, butoxypropyl, amyloxypropyl,methoxycarbonylethyl, ethoxycarbonylethyl, allyl or butoxycarbonylethyland, preferably, methyl, ethyl or β-cyanoethyl.

Individual meanings which are possible for the groups R₁, R₁ ' and R₂ 'are, for example, the following: C₁ -C₁₈ -alkyl groups, which areoptionally substituted by C₁ -C₄ alkoxy, hydroxyl, chlorine, bromine,cyano, carboxyl, carb-C₁ -C₄ -alkoxy, sulpho, carboxamide or acetoxy;examples which may be mentioned are methyl, butyl, propyl, ethyl, octyl,β-cyanoethyl, β-chloroethyl, β-hydroxyethyl, β-hydroxypropyl,β-hydroxy-γ-chloropropyl, β-carboxyethyl, β-carbomethoxyethyl,β-carboethoxyethyl or β-carbobutoxyethyl, β-carboxamidoethyl andβ-acetoxyethyl; as well as cycloaliphatic groups, such as cyclopentyl,methylcyclohexyl, trimethlcyclohexyl and, preferably, cyclohexyl; orphenyl, benzyl or phenethyl which are optionally substituted by C₁ -C₄-alkyl, such as methyl, lower alkoxy, such as methoxy, or halogen, suchas chlorine.

When it is used in connection with definitions, such as alkyl, alkoxy,carbalkoxy and the like, the term "lower" denotes that the alkylradicals which occur in the radical contain not more than 4 carbonatoms.

Examples of non-ionic substituents Z on the rings B and C are alkyl,alkoxy, halogen, nitro, alkylmercapto, alkylsulphonyl, arylsulphonyl,acylamino, cyano, carboxamide and sulphonamide, and alkyl is to beunderstood, in particular, as alkyl with 1 to 4 carbon atoms, such asmethyl, ethyl, isopropyl and n-butyl, alkoxy groups are to beunderstood, in particular, as those with 1 to 4 carbon atoms, such asmethoxy, ethoxy, n-propoxy, n-butoxy and isopropoxy, halogen radicalsare to be understood as, in particular, chlorine and bromine, inaddition to fluorine, alkylmercapto and alkylsulphonyl are to beunderstood, in particular, as those which have 1 to 4 carbon atoms inthe alkyl radical, such as methylmercapto, β-hydroxyethylmercapto,isopropylmercapto or n-butylmercapto or methylsulphonyl,β-hydroxy-ethylsulphonyl, isopropylsulphonyl or b-butylsulphonyl,arylsulphonyl is to be understood, in particular, as phenylsulphonyl,aralkylsulphonyl is to be understood as, preferably, benzylsulphonyl,acylamino is to be understood as, in particular, C₁ -C₄-alkylcarbonylamino, such as acetylamino, and C₁ -C₄-alkylsulphonylamino, such as methylsulphonylamino, and carboxamide andsulphonamide radicals are to be understoofd, in particular, ascarboxamide or sulphonamide radicals which are substituted by one or twoalkyl radicals which contain 1 to 4 carbon atoms, such as methyl, ethylor n-butyl.

Groups which confer solubility in water are, above all, sulphonic acidgroups and groups which have positively charged (quaternary) nitrogenatoms. It is true that free carboxyl groups (--COOH) are as a ruleincluded amongst the groups conferring solubility in water, but these asa rule effect solubility in water only in the form of their salts, forexample the alkali metal salts, so that their exclusion merelyrepresents a preferred embodiment.

Possible cations M are those of inorganic or organic bases, possibleinorganic cations being, in particular, alkali metal cations, such asNa, K and Li, and ammonium, and possible organic cations being, forexample, pyridinium, alkyl-ammonium and dialkyl-ammonium, in which thealkyl groups preferably have 1 to 4 carbon atoms, as well as cations ofbasic dyestuffs. Monosulphonated dyestuffs are preferred.

The reaction of the naphtholactam of the formula (II) with the compoundsof the formula (III) which contain an active methylene group is carriedout in the presence of an acid condensing agent, such as phosphorusoxybromide, phosphorus trichloride, phosphorus tribromide, phosphoruspentachloride, thionyl chloride, phosgene (in an autoclave) or mixturesof phosphorus oxychloride and phosphorus pentoxide, but especially inthe presence of phosphorus oxychloride.

The reaction is advantageously carried out with heating, for example attemperatures of 50° to 200° C., but preferably in a range from 60° to130° C. It is appropriately carried out in an inert organic solvent suchas benzene, toluene, xylene, chlorobenzene, dichlorobenzene,nitrobenzene, ethylene chloride, carbon tetrachloride or chloroform.

The condensation reaction of compound IV and V is carried out underalkaline reaction conditions, appropriately in an organic solvent, suchas methanol, ethanol, butanol, ethylene glycol monomethyl ether,dimethylformamide, pyridine or chlorobenzene, in the presence of acondensing agent having an alkaline reaction, such as triethylamine,potassium carbonate, sodium hydroxide or magnesium oxide, at elevatedtemperature, appropriately at 40° to 160° C. and preferably at 60° to100° C.

The starting materials of the formula (III) are accessible by a knownroute by reacting a naphtholatam compound of the formula (V) with adiphosphorus pentasulphide to give the corresponding thione compound andreacting the latter with quaternising agents R-An, preferably dimethylsulphate.

The optimal subsequent sulphonation of compounds of the formula I whichare free from sulphonic acid groups is appropriately carried out byreacting the compounds with customary sulphonating agents, preferablyoleum containing 5 to 60% of SO₃, one to two sulpho groups beingintroduced by this means. The reaction is appropriately carried attemperatures between 5° and 50° C. by methods which are in themselvesknown.

The optional nitration is carried out in the customary manner using amixture of nitric acid and sulphuric acid and halogenation is carriedout by means of the action of elementary bromine or chlorine.

A further route to the dyestuffs of the formula I consists in carryingout the condensation reaction with halogen-containing condensing agents,such as, in particular, phosphorus oxychloride, so that a --CO-halogenogroup, especially a chlorocarbonyl group, is formed in the 4-position ofthe naphtholactam and this group is subsequently reacted with alcohols,phenols, amines or mercaptans to give the corresponding esters, amidesor thio-esters.

Alcohols and phenols which are suitable for the reaction are, forexample, methanol, ethanol, n-propanol, i-propanol, butanol,sec.-butanol, iso-butanol, 1,2-dihydroxybutane, 2,5-dihydroxyhexane,3-methyl-1,5-dihydroxypentane, 2-ethyl-hexanol, 2,2-dimethylpentanol,2,2,4-trimethylpentanol, dodecyl alcohol, octadecyl alcohol, benzylalcohol, cyclohexanol, allyl alcohol, methallyl alcohol, cinnamylalcohol, lauryl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurylalcohol, diethylene glycol monomethyl ether or diethylene glycolmonoacetate, triethylene glycol monobutyl ether, ethylene glycol,1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,neopentyl glycol, 2,2-diethylpropane-1,3-diol,2-ethyl-2-butylpropane-1,3-diol, 2-ethyl-2-propylpropane-1,3-diol,2,2,4-trimethylhexane-1,6-diol, 2-ethyl-2-methylpropane-1,3-diol,1,10-decanediol, diethylene glycol, triethylene glycol,β,β'-thiodiethanol, 1,1-, 1,2-, 1,3- and 1,4-dimethylolcyclohexane and1,2-, 1,3- and 1,4-α,α'-xylene glycol; as well as phenol and mono- andpoly-alkylphenols, for example 2-, 3- or 4-methyl-, -ethyl-, -n-propyl-,-isopropyl-, -n-butyl-, -iso-butyl-, -tert.butyl-, -n- or -iso-pentyl-,-n- or -iso-dodecyl-, -n- or -iso-palmityl-, -n- or -iso-stearyl-,-ethane-, -propene-, -butene- and -ethine-phenol, 2,3-, 2,4-, 2,5- 2,6-3,4- or 3,5-dimethyl-, -diethyl- and -dipropyl-phenols, 2,3,4-, 2,3,5-,2,3,6-, 3,4,5- or 2,4,6-trimethyl-, -triethyl- and -tripropyl-phenols,2,3,5,6-, 2,3,4,5- or 2,3,5,6 -tetramethyl-, -tetraethyl- and-tetrapropyl-phenols and 2,3,4,5,6-pentamethyl-phenol, it also beingpossible for the abovementioned alkyl radicals to be mixed, for example2,6-dimethyl-4-tert.-butyl-phenol; cycloalkylphenols, for example 2-, 3-or 4-cyclohexyl-phenol; substituted alkylphenols, for example4-chloromethyl-, 4-hydroxymethyl- and 3-trifluoromethyl-phenol;aralkylphenols, for example 2-, 3- or 4-benzylphenols; arylphenols, forexample 2-, 3- or 4-hydroxy-diphenyl; alkylamino-, arylamino- andacylamino-phenols, for example 2-, 3- or 4-acetylamino-, 2-, 3- or4-benzoylamino-, 2-, 3- or 4-methacroylamino- andN-methyl-N-formyl-4-amino- phenol; halogenophenols, for example 2-, 3-or 4-chloro- or -bromo-phenol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dichloro(bromo)-phenol, 2-methyl-5-chloro-, 2-methyl-6-chloro-,3-methyl-4-chloro-, 5-methyl-2-chlor-, 2-methyl-4-chloro- or2-methyl-3-chloro-phenol and 3,5,3',5'-tetrchloro-2,2'-dihydroxydiphenyl; nitrophenols, for example 2-, 3- or 4-nitrophenol,2-methyl-5-nitro-, 4-methyl-2-nitro-, 3-methyl-4-nitro-,4-methyl-3-nitro- and 3,5-dimethyl-4-nitro-phenol; hydroxyphenylsuphonicacids and hydroxyphenylcarboxylic acids and their esters and amides, forexample 3- or 4-hydroxybenzoic acid or -benzenesulfonic acid, 2-, 3- or4-hydroxybenzoic acid (or -benzenesulphonic acid) methyl ester, propylester, isobutyl ester, phenyl ester, naphthyl ester and halogenophenylesters, 2-hydroxy-5-chlorobenzoic acid ester, 2-cyanato-3methyl-benzoicacid esters, 2-, 3- or 4-hydroxybenzoic acid dimethylamide,diethylamide, morpholylamide or piperidylamide; alkoxy-, aryloxy- andacyloxy-phenols, for example 2-, 3- or 4-methoxy-, -ethoxy-, -propoxy-,-isopropoxy-, -butoxy-, -phenoxy-, -acetoxy- and -benzoxy-phenols, N,N-dialkylcarbamate and 4-allyl-2-methoxyphenol; acylphenols, for example2-, 3- or 4-acetyl-, -propionyl- and -benzoyl-phenol and4-acetyl-1,3-dihydroxybenzene; cyanophenols, for example 2-, 3- or4-cyanophenol; phenols with S-containing substituents, for example 2-,3- or 4-methylmercapto-, -ethylmercapto-, -propylmercapto-,-phenylmercapto-, -acetylmercapto- and -benzoylmercapto-phenols, 3-or4-mercaptophenols, 2,4-bis- methylmercapto-3-methyl-phenyl and ##STR9##polyhydric phenols, such as, for example pyrocatechol, hydroquinone,resorcinol and the like; alkylated dihydroxyphenols, such as, forexample, 1,3-dihydroxy-4-methylbenzene or 1,2-dihydroxy-4-hexylbenzene;alkoxylated dihydroxyphenols, such as, for example,1,4-dihydroxy-3-hexoxybenzene; cycloaliphatic phenols, such as, forexample, p-cyclopentylphenol or p-cyclohexylphenol; halogenateddihydroxyphenols, such as, for example, phloroglucinol or pyrogallol;and polynuclear phenols, such as, for example,2,2-bis-(p-hydroxyphenyl)-propane, 4,4'-dihydroxydiphenyl,2,2'-dihydroxydiphenyl, 2,4'-dihydroxydiphenyl, 2,4'-dihydroxydiphenyland dihydroxynaphtahalenes, such as 2,6-dihydroxynaphthalene.Dihydroxyarylsulphones, for example bis-(p-hydroxyphenyl)-sulphone,2,4'-dihydroxydiphenylsulphone. 5'-chloro-2,4-dihydroxydiphenylsulphone,5'-chloro-2,4'-dihydroxydiphenylsulphone,3'-chloro-4,4'-dihydroxydiphenyl-sulphone andbis-(4-hydroxyphenyl)-biphenyldisulphone, can also be used.

Aromatic dihydroxy-ethers, for example p,p'-dihydroxydiphenyl ether,p,p'dihydroxytriphenyl ether, the 4,3'-, 4,2'-, 3,3'-, 2,2'- and2,3'-dihydroxydiphenyl ethers and 4,4'-dihydroxy-2,5-dimethyldiphenylether, are also suitable, as are the addition products of equimolaramounts of ethylene oxide and mercaptans, and also n-butylmercaptan,phenylmercaptan 2-, 3- or 4-chlorophenylmercaptan, 2,4- or2,5-dichlorphenylmercaptan, 2-, 3- or 4-methylphenylmercaptan, 2,4- or2,5-dimethylphenylmercaptan, 2-, 3- or 4-methoxyphenylmercaptan, 2,4- or2,5-dimethoxyphenylmercaptan, 2- or 4-nitrophenylmercaptan, 2- or4-carbomethoxyphenylmercaptan, 2-mercapto-benzthiazole,2-mercapto-6-chloro-benzthiazole, 2-mercapto-4-chloro-benzthiazole,2-mercapto-4-methyl-benzthiazole, 2-mercapto-6-methyl-benzthiazole,2-mercapto-6-methoxy-benzthiazole, 2-mercapto-6-ethoxy-benzthiazole,2-mercapto-benzoxazole and 2-mercaptobenzimidazole.

Compounds H₂ N--NR₃ R₄ which can be employed, optionally in the form oftheir salts, such as hydrochlorides, hydrobromides, hydroiodides,nitrates, sulphates or acetates, are, for example, the followinghydrazines and hydrazides and cyclohexanone hydrazone: methylhydrazine,isopropylhydrazine, phenylhydrazine, 2-nitrophenylhydrazine,3-nitrophenylhydrazine, 4-nitrophenylhydrazine,2,4-dinitrophenylhydrazine, 2-chlorophenylhydrazine, N-aminopiperidine,N-aminopyrrolidine, N-aminomorpholine, N-aminocarbazole,N-aminotetrahydro(iso)quinoline, methanesulphonic acid hydrazide,ethanesulphonic acid hydrazide, isopropanesulphonic acid hydrazide,hexanesulphonic acid hydrazide, cyclohexanesulphonic acid hydrazide, C₁-C₅ -alkanoylhydrazides, such as acetylhydrazide, benzoylhydrazide,benzenesulphonic acid hydrazide, 2-, 3- or 4-toluenesulphonic acidhydrazide, 2-, 3- or 4-chloro-(bromo- or fluoro-)benzenesulphonic acidhydrazide, 2-, 3- or 4-hydroxybenzenesulphonic acid hydrazide, 2, 3- or4-dimethylaminobenzenesulphonic acid hydrazide, 2-, 3- or4-nitrobenzenesulphonic acid hydrazide, 2-, 3- or4-methylmercapto-benzenesulphinic acid hydrazide, quinolinesulphonicacid hydrazides, carbazolesulphonic acid hydrazides,phenylpyrazolonesulphonic acid hydrazides and imidazolesulphonic acidhydrazides.

The naphtholactam compounds of the formula II which are employed asstarting materials are obtainable by reacting oxylylene dicyanide withglyoxal in the presence of a base (NaOH or KOH) and a solvent attemperature below 50° C. (for example 0° to 40° C.) to give1,4-dicyanonaphthalene and subsequently either a) saponifying the1,4-dicyanonaphthalene in a basic or, preferably, acid medium to givethe 1,4-dicarboxylic acid and either converting the1,4-naphthalene-dicarboxylic acid into a functional derivative and thenconverting the latter, using a 10 to 50% excess of nitric acid, to the8-nitro-1,4-naphthalene-dicarboxylic acid derivative and reducing thisto the 8-amino derivtive, or nitrating the 1,4-naphthalenedicarboxylicacid direct and subsequently reducing the reaction product to the8-amino-naphthalene-1,4-dicarboxylic acid, and then converting the8-amino derivative into the 1,8-naphtholactam-4-carboxylic acid, orfunctional derivatives thereof, either by spontaneous cyclisation or bywarming, or b) nitrating the 1,4-dicyanonaphthalene in the 8-positionusing a 10 to 50% excess of nitric acid and subsequently reducing thenitro group to the 8-amino group, effecting naphtholactam cyclisation byspontaneous formation or by warming and saponifying the cyano group inthe 4-position, if this has not already been saponified during thereduction of the 8-nitro group, in a basic or acid medium, optionallyvia the stage of the 4-carboxamido-1,8-naphtholactam.

The naphtholactams which carry an organic group as the substituent R onthe lactam ring are obtained, for example, by alkylating thecorresponding naphtholactams which carry hydrogen on the nitrogen atomof the lactam ring (R═H) in a polar aprotic solvent, such asdimethylformamide or N-methylpyrrolidone, with a toluenesulphonic acidester of the formula ##STR10## in the presence of a strong base, such assodium hydroxide or potassium hydroxide.

R has the same meaning as above.

Preferred starting compounds of the formula III which contain an activemethylene group are the azole-acetic acid derivatives of the formula##STR11## in which Y denotes a --S-- or --O-atom or a --NR"-group andthe ring B can carry non-ionic substituents or optionally substitutedfused rings, possible substituents for ring B being, for example, one ormore halogen atoms, which in this context are generally to be understoodas, in particular, chlorine atoms or bromine atoms, lower alkoxy groups(for example methoxy, ethoxy, propoxy or butoxy groups), or hydroxyl,cyano, vinyl, nitro, lower alkylamino, dialkylamino, phenylamino,N-phenyl-N-alkylamino, phenyl, phenoxy, acyl, acyloxy or acylaminogroups. Lower alkyl groups, especially unsubstituted methyl and ethylgroups, are particularly preferred.

Examples of suitable compounds of the formula VI which may be mentionedare: benzoxazole-2-yl-acetic acid esters, methyl5-methyl-benzoxazol-2-yl-acetate, n-propyl4,5-dimethylbenzoxazol-2-yl-acetate, ethyl5-chloro-benzoxazol-2-yl-acetate, methoxyethyl5-bromobenzoxazol-2-yl-acetate, ethylnaphth-[1,2-d]-oxazol-2-yl-acetate, methylnaphth-[2,3-d]-oxazol-2-yl-acetate, ethyl5-ethylsulphonyl-benzoxazol-2-yl-acetate, benzoxazol-2-yl-acetamide,5-methylbenzoxazol-2-yl-acetamide, 5-chloro-benzoxazol-2-yl-acetamide,5-ethylsulphonyl-benzoxazol-2-yl-acetamide,5-dimethylaminosulphonyl-benzoxazol-2-yl-acetamide,5-methyl-benzoxazol-2-yl-acetic acid methylamide,4,5-dimethyl-benzoxazol-2-yl-acetic acid methylamide,5-cyclohexyl-benzoxazol-2-yl-acetic acid cyclohexylamide,5-phenylbenzoxazol-2-yl-acetic acid isophorylamide,naphth-[1,2-d]-oxazol-2-yl-acetic acid methylamide,5-methoxybenzoxazol-2-yl-acetic acid n-propylamide,5-bromo-benzoxazol-2-yl-acetic acid methylamide,5-benzyl-benzoxazol-2-yl-acetic acid methylamide,5-(1',1',3',3'-tetramethyl-n-butyl)-benzoxazol-2-yl-acetic acid anilide,5-phenylsulphonyl-benzoxazol-2-yl-acetic acid anilide,5-benzylsulphonyl-benzoxazol-2-yl-benzoxazol-2-yl-acetic acidmethylamide, 5-diethylaminocarbonyl-benzoxazol-2-yl-acetic acidn-butylamide, 5-methoxy-benzoxazol-2-yl-acetic acid cyclohexylamide,5-ethoxy-benzoxazol-2-yl-acetic acid anilide,5-phenoxybenzoxazol-2-yl-acetic acid anilide,5-acetylamino-benzoxazol-2-yl-acetic acid 3'-methoxy-n-propylamide,5-chloro-benzoxazol-2-yl-acetic acid methylamide, benzoxazol-2-yl-aceticacid n-propylamide, 5-methyl-benzoxazol-2-yl-acetic acid ethylamide,5-methyl-benzoxazol-2-yl-acetic acid n-propylamide,5-methylbenzoxazol-2-yl-acetic acid 2'-hydroxy-ethylamide,5-methylbenzoxazol-2-yl-acetic acid 3'-methoxy-n-propylamide,5-methylbenzoxazol-2-yl-acetic acid 2'-bromoethylamide,5-methylbenzoxazol-2-yl-acetic acid isobutylamide,5-methyl-benzoxazol-2-yl-acetic acid n-hexylamide,5-methyl-benzoxazol-2-yl-acetic acid benzylamide,5-methyl-benzoxazol-2-yl-acetic acid anilide,5-methyl-benzoxazol-2-yl-acetic acid dimethylamide,5-methyl-benzoxazol-2-yl-acetic acid diethylamide,5-methyl-benzoxazol-2-yl-acetic acid di-n-butylamide,5-methyl-benzoxazol-2-yl-acetic acid aziridide,5-methyl-benzoxazol-2-yl-acetic acid pyrrolidide,5-methyl-benzoxazol-2-yl-acetic acid piperidide,5-methyl-benzoxazol-2-yl-acetic acid piperazide,5-methyl-benzoxazol-2-yl-acetic acid morpholide, ethylbenzthiazol-2-yl-acetate, methyl 6-methyl-benzthiazol-2-yl-acetate,n-propyl 6-methoxybenzthiazol-2-yl-acetate, ethyl6-ethoxybenzthiazol-2-yl-acetate, methyl6-chloro-benzthiazol-2-yl-acetate, ethylnaphth-[1,2-d]-thiazol-2-yl-acetate, benzthiazol-2-yl-acetamide,6-methylbenzthiazol-2-yl-acetic acid methylamide,6-chloro-benzthiazol-2-yl-acetic acid ethylamide,6-methoxybenzthiazol-2-yl-acetic acid morpholide,6-ethoxy-benzthiazol-2-yl-acetic acid dimethylamide,bis-benzoxazolyl-methane, bis-(5-methyl-benzoxazolyl)-methane,bis-(5,6-dimethyl-benzoxazolyl)-methane,bis-(5-chlorobenzoxazolyl)-methane, bis-(5-bromobenzoxazolyl)-methane,bis-(5-fluoro-benzoxazolyl)-methane,bis-(5-ethylsulphonylbenzoxazolyl)-methane, bis-(5-tertiarybutyl-benzoxazolyl)-methane, bis-(5-ethyl-benzoxazolyl)-methane,bis-(5-cyclohexylbenzoxazolyl)-mthane,bis-(5-phenyl-benzoxazolyl)-methane,bis-(6-methoxy-benzoxazolyl)-methane,bis-(5-benzylbenzoxazolyl)-methane,bis-(5-dimethylaminosulphonyl-benzoxazolyl)-methane,bis-(5-diethylaminocarbonyl-benzoxazolyl)-methane,bis-(5-ethoxy-benzoxazolyl)-methane,bis-(5-phenoxy-benzoxazolyl)-methane,bis-(5-acetylamino-benzoxazolyl)-methane, bis-benzthiazolyl-methane,bis-(6-methyl-benzthiazolyl)-methane,bis-(6-methoxybenzthiazolyl)-methane,bis-(6-chloro-benzthiazolyl)-methane,benzimidazolyul-5-methyl-benzoxazolyl-methane,benzimidazolyl-benzthiazolyl-methane,benzthiazolyl-5-methyl-benzoxazolyl-methane,5-methyl-benzimidazolyl-2-benzoxazolyl-methane,1-methyl-benzimidazolyl-5-phenyl-benzoxazolyl-methane,1-β-cyano-ethyl-benzimidazolyl-5-cyclohexyl-benzoxazolyl-methane,1-ethyl-benzimidazolyl-5-chloro-benzoxazolyl-methane,5-methyl-benzoxazolyl-acetamide-6-sulphonic acid,benzthiazolyl-acetamide-5-or -6-sulphonic acid,bis-(5-methyl-6-sulphobenzoxazolyl)-methane,5-methylbenzoxazolyl-phenylsulphonyl-methane,benzthiazolyl-phenylsulphonylmethane,benzthiazolyl-benzylsulphonylmethane,benzthiazolylmethylsulphonylmethane,benzthiazolyl(p-methylphenyl)-sulphonylmethane,benzoxazolyl-(p-methylphenyl)-sulphonylmethane,benzthiazolyl-(p-chlorophenyl)-sulphonyl-methane,benzthiazolyl-(p-methoxy)-sulphonylmethane,benzthiazol-2-yl-acetamide-6-sulphonic acid,benzoxazol-2-yl-acetamide-6-sulphonic acid, benzimidazolyl-acetonitrile,methylbenzimidazolyl-acetonitrile, dimethylbenzimidazolyl-acetonitrile,chlorobenzimidazolyl-acetonitrile,, nitrobenzimidazolyl-acetonitrile,ethoxycarbonylbenzimidazolyl-acetonitrile,cyanobenzimidazolyl-acetonitrile, naphthimidazolyl-acetonitrile,benzimidazolyl-acetic acid esters and benzimidazolyl-acetic acid amides.

Compounds which have an active methylene group and contain 2heterocyclic groups are, for example, those of the formula ##STR12## inwhich Z has the same meaning as above.

Further valuable heterocyclic compounds which have an active methylenegroup are, for example, also those of the formulae ##STR13## in whichthe aryl radical is, for example, a phenyl radical or a phenyl radicalsubstituted by C₁ -C₃ -alkyl or C₁ -C₃ -alkoxy and ##STR14##

A further preferred group comprises the cyanoacetic acid derivatives,such as, for example, C₁ -C₅ -alkyl cyanoacetates, such as NC--CH₂--CO--O--(CH₃, C₂ H₅, C₃ H₇ or C₄ H₉), cyanoacetic acid hydrazide,cyanoacetamide and its N-alkylated and N-arylated derivatives,2-cyanoacetanilide, cyanoacetylurea, cyanoacetylurethanes, such asNC--CH₂ --CO--NH--CO--O(CH₃ or C₄ H₉), and ω-cyanoacetophenones, such asNC--CH₂ ═CO--C₆ H₅ and NC--CH₂ --CO--C₆ H₄ --COOH(--o).

The dyestuffs of the formula (I) give brillant, luminous orange-to-reddyeings which usually fluoresce in UV light and have outstandingfastness properties in use, the dyestuffs which are free from groupsconferring solubility in water being especially valuable.

The new dyestuffs are preferably free from sulphonic acid groups and aresuitable for dyeing semi-synthetic and fully synthetic fibres, such asacrylic fibres or acrylonitrile fibres, polyacrylonitrile fibres andcopolymers of acrylonitrile and other vinyl compounds; such asacrylates, acrylamides, vinylpyridine, vinyl chloride or vinylidenechloride, copolymers of dicyanoethylene and vinyl acetate and alsoacrylonitrile block copolymers, fibres made of polyurethanes,polyolefines, such as base-modified, nickel-modified or unmodifiedpolypropylene, and cellulose triacetate and cellulose 21/2 acetate andespecially fibres made of polyamides such as Nylon-6, Nylon-6,6 or Nylon12, and fibres made of aromatic polyesters, such as those ofterephthalic acid and ethylene glycol or 1,4-dimethylolcyclohexane andcopolymers of terephthalic acid and isophthalic acid and ethyleneglycol.

Dyeing of the said fibre materials with the dyestuffs, which preferablyare sparingly soluble in water, is preferably effected from an aqueousdispersion.

It is therefore appropriate finely to divide those dyestuffs which canbe used as disperse dyestuffs, by grinding with textile auxiliaries,such as, for example, dispersing agents and possibly grindingauxiliaries. Subsequent drying gives dyestuff formulations which consistof the textile auxiliary and the dyestuff.

Examples which may be mentioned of dispersing agents, of the non-ionicgroup, which can advantageously be used are: addition products of 8 molsof ethylene oxide with 1 mol of p-tert.-octylphenol, of 15 or 6 mols ofethylene oxide with castor oil and of 20 mols of ethylene oxide with thealcohol C₁₆ H₃₃ OH, addition products of ethylene oxide withdi-[α-phenylethyl]-phenols, polyethylene oxide tert.-dodecyl thioethers,polyamine polyglycol ethers or addition products of 15 or 30 mols ofethylene oxide with 1 mol of the amine C₁₂ H₂₅ NH₂ or C₁₈ H₃₇ NH₂.

Anionic dispersing agents which may be mentioned are: sulphuric acidesters of alcohols of the fatty series with 8 to 20 carbon atoms, of theethylene oxide adducts of the corresponding fatty acid amides, or ofalkylated phenols with 8 to 12 carbon atoms in the alkyl radical;sulphonic acid esters containing alkyl radicals with 8 to 20 carbonatoms; sulphation products of unsaturated fats and oils; phosphoric acidesters containing alkyl radicals with 8 to 20 carbon atoms; fatty acidsoaps and also alkylarylsulphonates, condensation products offormaldehyde and naphthalenesulphonic acid and ligninsulphonates.

Suitable cationic dispersing agents are quaternary ammonium compoundswhich contain alkyl or aralkyl radicals with 8 to 20 carbon atoms.

In addition to the dispersing agents, the dyestuff formulations can alsocontain organic solvents, especially solvents which boil above 100° C.and which preferably are miscible with water, such as mono- anddi-alkylglycol ethers, dioxane, dimethylformamide or dimethylacetamide,tetramethylenesulphone or dimethylsulphoxide. The dyestuff, thedispersing agent and the solvent can advantageously be ground together.

A dyestuff formulation of this type is manufactured, for example, bymixing 2 to 30, and preferably 5 to 20, percent by weight of thedispersing agent to a paste with 10 to 55 percent by weight, andpreferably approximately the two-fold to four-fold amount, of thedyestuff and about 10 to 20 parts of a glycol or of anotherwater-retaining agent. Subsequently, for example, the pH value isadjusted to about 9 with a dilute acid, preferably with sulphuric acidor acetic acid, and the mixture is then made up to 100% with water. Themixture is then ground to the necessary fineness, for example in a glassmill or another dispersing apparatus, and during this operation thegrinding temperature can be between 20° and 90° C.

The dyeing of the polyester fibres with the dyestuffs according to theinvention, which are sparingly soluble in water, from an aqueousdispersion is carried out by the processes customary for polyestermaterials. Polyesters of aromatic polycarboxylic acids with polyhydricalcohols are preferably dyed at temperatures of above 100° C. underpressure. However, dyeing can also be carried out at the boiling pointof the dye bath in the presence of colour-transfer agents, for examplephenylphenols, polychlorobenzene compounds or similar auxiliarie,s, orcan be effected by the thermosol process, that is to say padding withsubsequent hot after-treatment, for example thermofixing, at 180° to210° C.

Cellulose 21/2-acetate fibres are preferably dyed at temperatures of 80°to 85° C., whilst cellulose triacetate fibres are advantageously dyed atthe boiling point of the dye bath. The use of colour-transfer agents canbe dispensed with when dyeing cellulose 21/2-acetate fibres or polyamidefibres. Dyestuffs according to the invention can also be used forprinting the said materials by customary methods.

The dyeings obtained according to the present process can be subjectedto an after-treatment, for example by heating with an aqueous solutionof a non-ionic washing agent.

According to the present process it is also possible to apply theindicated compounds by printing, instead of by impregnating. For thispurpose, for example, a printing ink which contains the finely disperseddyestuffs in addition to the auxiliaries customary in printing, such aswetting agents and thickeners, is used.

Furthermore, for example, synthetic fibres, such as polyesters andpolyamides, can be dyed in organic solvent liquors, such as in a mixtureof perchloroethylene and dimethylformamide or in pure perchloroethylene.

Deep, luminous dyeings and prints with excellent fastness propertie,s,especially fastness to light, thermofixing, sublimation, pleating, fluegas, cross-dyeing, dry-cleaning, ironing, rubbing, chlorine and setprocessing, such as fastness to water, washing and perspiration, areobtained by the present process.

The new dyestuffs, which are insoluble in water, can also be used forspin-dyeing polyamides, polyesters and polyolefines. The polymer to bedyed is appropriately mixed, in the form of a powder, granules or chips,as a ready-to-use spinning solution or in the molten state with thedyestuff, which is introduced in the dry state or in the form of adispersion or solution in an optionally volatile solvent. Afterhomogeneous dispersion of the dyestuff in the solution or melt of thepolymer, the mixture is processed in a known manner by casting, pressingor extruding to fibres, yarns, monofilaments, films and the like.

The dyestuffs according to the invention are outstandingly suitable forcolouring macromolecular materials, such as lacquers, films, sheets andmouldings, for example those made of cellulose esters, such as cellulose21/2-acetate and cellulose triacetate, polyvinyl compounds, such aspolyvinyl chloride and polyvinyl acetate; polyurethanes, polystyrene,polyesters, polyamides and polycarbonates in bulk. The dyestuffs whichcan be used for this application are, in particular, the compounds ofthe formula I which are not in the form of a salt and also those whichcontain sulpho groups and are in the form of salts of suitable organiccations, such as, for example, those of alkylamines which solubilisefats or of basic dyestuffs.

The dyestuffs according to the invention possess high fastness to light,even in light dyeings and in combination with other disperse dyestuffs,high brilliance (fluorescence), high fastness to sublimation, a lowsensitivity to carriers in respect of the fastness to light and a highdepth of colour, coupled with a good reserve for other fibres, forexample wool fibres. They also have only a low sensitivity to changes inpH and are especially suitable for the high temperature process and thethermosol process as well as for permanent press finishing ("Koratron"process). They are also suitable for printing by all customaryprocesses, including, inter alia, for the printing of mixed fabrics.

The possess a high fastness to light, good stability to heat and goodsolubility, even in the case of bulk dyeings (especially polyesterspinning compositions). Coupled with a high fastness to sublimation,they display no migration on the surface when the fibres are subjectedto heat treatments (for example on texturing) and display good fastnessto rubbing.

The sulphonated representatives of the dyestuffs according to theinvention are in the main used for dyeing wool and synthetic polyamidesand, for this purpose, aqueous solutions which contain textileauxiliaries, such as, for example, levelling agents, are used.

In the example which follow, parts denote parts by weight, unlessotherwise stated, percentages denote percentages by weight and thetemperatures are given in degrees Centigrade.

Preparation of the Starting Materials

(a) 15.6 parts by weight of o-xylylene dicyanide and 8.5 parts by weightof glyoxal hydrate (trimer) (3 C₂ H₂ O₂.2H₂ O) containing 80% of glyoxalto be liberated are stirred into 200 parts by volume of methanol. 11.2parts by weight of powdered potassium hydroxide are added in portions tothe reaction mixture, at 15°, whilst stirring and under nitrogen.

After the potassium hydroxide has been added, the reaction mixture isstirred for a further 15 hours at room temperature and under nitrogen.The slightly brown-coloured reaction mixture is then freed from methanolin vacuo and diluted with 500 parts by volume of water. The crude1,4-dicyanonaphthalene which has precipitated is filtered off and washedwith water until neutral. 11 parts by weight (61.8% of theory) of1,4-dicyanonaphthalene are obtained in the form of slightlybrown-coloured small needles with a melting point of 175° to 185° C.

After recrystallising once from alcohol with the aid of 5 parts byweight of active charcoal, 5.5 parts by weight of the compound ##STR15##are obtained in the form of beautiful needles with a melting point of204° to 205° C.

(b) 46.4 g of technical grade naphthalene-1,4-dicarboxylic acid (93%pure) are introduced at a temperature of 20° to 25° into a stirred flaskwhich contains 480 g of 93% strength sulphuric acid, whilst stirring.The resulting thick suspension is cooled to 0° and a mixture consistingof 22 g of 63% strength nitric acid and 22 g of 93% strength sulphuricacid is allowed to run in dropwise in the course of 30 minutes at 0° to2°, with external cooling. The mixture is then stirred for a further 5hours at 0° to 5° and is then poured onto 1 kg of fine ice. The productwhich has precipitated is filtered off using a suction filter and iswashed with water until neutral, after which the resulting product ofthe formula ##STR16## is dried in vacuo at 70°. Yield 45 g.

For purification, 45 g of the crude product are heated briefly to theboil with 225 ml of glacial acetic acid, the mixture is then allowed tocool and the product which has precipitated is filtered off at roomtemperature. This gives the nitro compound in the form of a pale greypowder which dissolves completely in water when sodium carbonate isadded. Melting point 252°.

(c) 52 parts of 8-nitro-naphthalene-1,4-dicarboxylic acid are dissolvedin 700 parts of absolute ethyl alcohol and the solution is boiled underreflux for 12 hours whilst continuously passing in hydrogen chloridegas. The resulting solution is evaporated in vacuo. The4-ethoxycarbonyl-8-nitro-naphthalene-1-carboxylic acid of the formula##STR17## which is obtained in this way, melts at 178° to 180°.

If the monoester is hydrogenated, the 4-ethoxycarbonyl-1,8-naphtholactamdescribed above is obtained and this confirms that the esterification ofthe carboxylic acid group has taken place in the 4-position.

(d) 130 parts of 8-nitro-naphthalene-1,4-dicarboxylic acid are dissolvedin 500 parts of dimethylformamide, 40 parts of sodium hydroxide areadded and after stirring for 30 minutes 170 parts by volume of diethylsulphate are added all at once. The temperature then rises to 90°. Themixture is stirred for 2 hours, paying no attention to the temperature,a small amount of impurities is then filtered off from the solution andthe filtrate is discharged into 2,500 parts by volume of a 10% strengthsodium chloride solution and 50 parts by volume of a 30% strength sodiumhydroxide solution. After stirring briefly, diethyl8-nitro-naphthalene-1,4-dicarboxylate with a melting point of 107° to109° is filtered off, washed and dried.

(e) 32 parts of diethyl 8-nitro-naphthalene-1,4-dicarboxylate arestirred into 200 parts of glacial acetic acid and, after adding 20 partsof iron powder, the mixture is boiled under reflux for 6 hours. Forworking up, the mixture is filtered hot, the filtrate is diluted with anequal volume of water and the 4-ethoxycarbonyl-1,8-naphtholactam whichis thus precipitated is filtered off, washed until neutral and dried.The product of the formula ##STR18## which is obtained in good yield,melts at 216° to 218°. Analysis gave the following values

    ______________________________________                                                      C       H        N                                              ______________________________________                                        calculated:     69.7      4.6      5.8                                        found:          69.3      4.5      5.6                                        ______________________________________                                    

(f) 29 parts of dimethyl 8-nitro-naphthalene-1,4-dicarboxylate (whichcan be prepared analogously to Example 5 using dimethyl sulphate) aredissolved in 500 parts of ethyl acetate and hydrogenated with Raneynickel. 4-Methoxycarbonyl-8-amino-1-naphtholactam precipitates outvirtually completely. After the hydrogenation has ended, the mixture isfiltered and the residue is extracted with methylglycol. Evaporated ofthe extraction solution gives the ester of the formula ##STR19## with amelting point of 264° to 266°. Analysis gave the following values:

    ______________________________________                                                    C        H         N                                              ______________________________________                                        calculated:   68.72      3.99      6.17                                       found:        68.5       4.0       5.9                                        ______________________________________                                    

(g) 24 parts of 4-ethoxycarbonyl-8-amino-1-naphtholactam are boiled in180 partfs of water and 20 parts of a 30% strength sodium hydroxidesolution for one hour under reflux, during which time everything goesinto solution. This solution is filtered with charcoal whilst still hotand the filtrate is acidified. The 8-amino-1-naphtholactam-4-carboxylicacid which has precipitated is filtered off after cooling and washedwith water and dried.

(h) 44 parts of naphthalene-1,4-dicarboxylic acid are introduced inportions into 900 parts of concentrated sulphuric acid and the mixtureis stirred to give a homogeneous suspension. A few crystals of iodineand 36 parts of bromine are then added and the whole is stirredovernight at room temperature. For working up, the mixture is dischargedonto ice and filtered and the product is washed with water untilneutral. 8-Bromo-naphthalene-1,4-dicarboxylic acid, which is thusobtained, can be purified by recrystallisation from glacial acetic acid.Melting point 288°-290°.

    ______________________________________                                                     C       H         Br                                             ______________________________________                                        calculated:    48.84     2.39      27.08                                      found:         48.81     2.43      26.41                                      ______________________________________                                    

(i) 60 parts of 8-bromo-naphthalene-1,4-dicarboxylic acid are introducedinto 560 parts of concentrated sulphuric acid and a mixture of 14 partsof a 98% strength nitric acid and 20 parts of concentrated sulphuricacid is added dropwise in the course of one hour, at 20°-25°, whilststirring. A solution forms transiently and some of the5-nitro-8-bromo-naphthalene-1,4-dicarboxlyic acid then precipitates out.This is separated off by discharging the reaction mixture onto ice,filtering off the precipitate, washing it until neutral and drying. Theresulting product was analysed in the form of dimethyl5-nitro-8-bromo-naphthalene-1,4-dicarboxylate. Melting point 115°-117°.

    ______________________________________                                                     C       H         N                                              ______________________________________                                        calculated:    45.68     2.74      3.80                                       found:         45.55     2.84      3.95                                       ______________________________________                                    

(j) 37 parts of dimethyl 5-nitro-8-bromo-naphthalene-1,4-dicarboxylateare stirred into 250 parts by volume of glacial acetic acid and, afteradding 20 parts of iron powder, the mixture is kept under reflux forfour hours. After cooling to room temperature, the residue is filteredoff and dried under reflux in 200 parts by volume of water and 80 partsby volume of a 30% strength sodium hydroxide solution for two hours. Themixture is filtered hot and 4-bromo-naphtholactam-5-carboxylic acid isprecipitated by acidifying the filtrate. The methyl ester of thiscompound has a melting point of 263°-265°.

In the following Examples and tables, the simple hexagon in each caserepresents the unsaturated aromatic benzenoid necleus unless otherwiseindicated by the symbol H; in which case the ring is saturated.

EXAMPLE 1

A mixture consisting of 5.40 g of 5-isobutoxycarbonyl-naphtholactam,3.50 g of benzthiazolyl-acetonitrile and 30 ml of chlorobenzene isstirred at 100° and a mixture of 3 ml of chlorobenzene and 2.10 ml ofphosphorus oxychloride is allowed to run in dropwise in the course ofabout 30 minutes. The mixture is stirred for a further 30 minutes at thesame temperature, after which it is allowed to cool. The precipitateformed is filtered off and washed with chlorobenzene and then withpetroleum ether. The material on the filter is then suspended in 25 mlof isopropanol, the suspension is heated to 60° and about 32 ml of a 10%strength sodium bicarbonate solution are added to give a pH value of 8.The mixture is allowed to cool and the dyestuff of the formula ##STR20##which has been liberated, is filtered off at 50°, washed withisopropanol and then dried at 70°.

When applied as a disperse dyestuff at 130°, the dyestuff dyes fabricmade of polyethylene terephthalate brilliant bluish-tinged red. Thedyeings possess good fastness to sublimation and light.

If, with an otherwise identical procedure, equivalent amounts of thenaphtholactam compounds listed under I in the table which follows areused in place of the naphtholactam compound mentioned initially andequivalent amounts of the compounds of column II, which have an activemethylene group, are used in place of benzthiazolyl-acetonitrile,dyestuffs with similar properties are obtained.

                                      TABLE                                       __________________________________________________________________________                                                             IV                                                                            Shade on                               II                                     poly-                   I              Compound having an                     ethylene                Naphtholactam  active methylene   III                 tereph-              No.                                                                              compound       group              Dyestuffs           thalate              __________________________________________________________________________        ##STR21##                                                                                    ##STR22##                                                                                        ##STR23##          red                  2                                                                                 ##STR24##     "                                                                                                 ##STR25##          "                    3                                                                                 ##STR26##     "                                                                                                 ##STR27##          "                    4                                                                                 ##STR28##     "                                                                                                 ##STR29##          "                    5                                                                                 ##STR30##     "                                                                                                 ##STR31##          "                    6                                                                                 ##STR32##     "                                                                                                 ##STR33##          violet               7                                                                                 ##STR34##     "                                                                                                 ##STR35##          "                    8                                                                                 ##STR36##     "                                                                                                 ##STR37##          red                  9                                                                                 ##STR38##                                                                                    ##STR39##                                                                                        ##STR40##          "                    10                                                                                ##STR41##                                                                                    ##STR42##                                                                                        ##STR43##          "                    11                                                                                ##STR44##     "                                                                                                 ##STR45##          "                    12                                                                                ##STR46##     "                                                                                                 ##STR47##          "                    13                                                                                ##STR48##     "                                                                                                 ##STR49##          "                    14                                                                                ##STR50##     "                                                                                                 ##STR51##          "                    15                                                                                ##STR52##     "                                                                                                 ##STR53##          "                    16 "                                                                                             ##STR54##                                                                                        ##STR55##          "                    17                                                                                ##STR56##     "                                                                                                 ##STR57##          "                    18                                                                                ##STR58##     "                                                                                                 ##STR59##          "                    19                                                                                ##STR60##     "                                                                                                 ##STR61##          "                    20                                                                                ##STR62##     "                                                                                                 ##STR63##          "                    21                                                                                ##STR64##     "                                                                                                 ##STR65##          "                    22 "                                                                                             ##STR66##                                                                                        ##STR67##          "                    23                                                                                ##STR68##     "                                                                                                 ##STR69##          "                    24                                                                                ##STR70##     "                                                                                                 ##STR71##          "                    25                                                                                ##STR72##     "                                                                                                 ##STR73##          "                    26                                                                                ##STR74##     "                                                                                                 ##STR75##          "                    27 "                                                                                             ##STR76##                                                                                        ##STR77##          "                    28                                                                                ##STR78##     "                                                                                                 ##STR79##          "                    29 "                                                                                             ##STR80##                                                                                        ##STR81##          "                    30                                                                                ##STR82##     "                                                                                                 ##STR83##          "                    31 "                                                                                             ##STR84##                                                                                        ##STR85##          "                    32 "                                                                                             ##STR86##                                                                                        ##STR87##          "                    33                                                                                ##STR88##     "                                                                                                 ##STR89##          "                    34 "                                                                                             ##STR90##                                                                                        ##STR91##          "                    35                                                                                ##STR92##     "                                                                                                 ##STR93##          "                    36 "                                                                                             ##STR94##                                                                                        ##STR95##          "                    37                                                                                ##STR96##                                                                                    ##STR97##                                                                                        ##STR98##          "                    38 "                                                                                             ##STR99##                                                                                        ##STR100##         "                    39                                                                                ##STR101##    "                                                                                                 ##STR102##         "                    40 "                                                                                             ##STR103##                                                                                       ##STR104##         "                    41                                                                                ##STR105##                                                                                   ##STR106##                                                                                       ##STR107##         "                    42                                                                                ##STR108##    "                                                                                                 ##STR109##         "                    43 "                                                                                             ##STR110##                                                                                       ##STR111##         "                    44                                                                                ##STR112##    "                                                                                                 ##STR113##         "                    45                                                                                ##STR114##                                                                                   ##STR115##                                                                                       ##STR116##         orange               46                                                                                ##STR117##    "                                                                                                 ##STR118##         "                    47                                                                                ##STR119##    "                                                                                                 ##STR120##         "                    48                                                                                ##STR121##    "                                                                                                 ##STR122##         "                    49                                                                                ##STR123##                                                                                   ##STR124##                                                                                       ##STR125##         "                    50                                                                                ##STR126##    "                                                                                                 ##STR127##         "                    51                                                                                ##STR128##    "                                                                                                 ##STR129##         "                    52                                                                                ##STR130##    "                                                                                                 ##STR131##         "                    53                                                                                ##STR132##                                                                                   ##STR133##                                                                                       ##STR134##         "                    54                                                                                ##STR135##    "                                                                                                 ##STR136##         "                    55                                                                                ##STR137##    "                                                                                                 ##STR138##         "                    56                                                                                ##STR139##    "                                                                                                 ##STR140##         "                    57                                                                                ##STR141##                                                                                   ##STR142##                                                                                       ##STR143##         red                  58 "                                                                                             ##STR144##                                                                                       ##STR145##         "                    59                                                                                ##STR146##    HCCH.sub.2CN                                                                                      ##STR147##         yellow               60                                                                                ##STR148##    "                                                                                                 ##STR149##         "                    61                                                                                ##STR150##    "                                                                                                 ##STR151##         "                    62 "              NCCH.sub.2COOC.sub.2 H.sub.5                                                                      ##STR152##         "                    63 "              NCCH.sub.2COOC.sub.2 H.sub.4OCH.sub.3                                                             ##STR153##         "                    64                                                                                ##STR154##    NCCH.sub.2CN                                                                                      ##STR155##         "                    65                                                                                ##STR156##    "                                                                                                 ##STR157##         "                    66                                                                                ##STR158##                                                                                   ##STR159##                                                                                       ##STR160##         "                    67 "                                                                                             ##STR161##                                                                                       ##STR162##         "                    68                                                                                ##STR163##    "                                                                                                 ##STR164##         "                    69                                                                                ##STR165##    "                                                                                                 ##STR166##         "                    70                                                                                ##STR167##                                                                                   ##STR168##                                                                                       ##STR169##         red                  71                                                                                ##STR170##    "                                                                                                 ##STR171##         "                    72                                                                                ##STR172##    "                                                                                                 ##STR173##         "                    73                                                                                ##STR174##    "                                                                                                 ##STR175##         "                    74                                                                                ##STR176##    "                                                                                                 ##STR177##         "                    75                                                                                ##STR178##    "                                                                                                 ##STR179##         "                    76                                                                                ##STR180##                                                                                   ##STR181##                                                                                       ##STR182##         "                    77                                                                                ##STR183##    "                                                                                                 ##STR184##         "                    __________________________________________________________________________

EXAMPLE 2

A mixture of 4.30 g of naphtholactam-5-carboxylic acid, 3.80 g ofbenzthiazolyl-acetonitrile and 50 ml of chlorobenzene is stirred at 100°and a mixture of 6.30 ml of phosphorus oxychloride and 6 ml ofchlorobenzene is allowed to run in dropwise in the course of about 30minutes and the mixture is then stirred at the same temperature for afurther 2 hours. After cooling, the precipitate, consisting of theproduct of the formula ##STR185## is filtered off and washed withchlorobenzene and strong suction is then applied to the material on thefilter.

The dyestuff acid chloride is now suspended in 50 ml of isobutanol andthe mixture is heated to the reflux temperature for 2 hours. Aftercooling, the dyestuff of the formula ##STR186## which has formed isisolated by filtration and washed with isobutanol, then with methanoland finally with water. The resulting dyestuff is identical to thatprepared according to Example 1.

If, with an otherwise identical procedure, the glycols listed under I inthe table which follows are used in place of isobutanol, the dyestuffsof column II are obtained.

    __________________________________________________________________________    I                   II                                                        Glycols             Dyestuffs                                                 __________________________________________________________________________    1  HOCH.sub.2 CH.sub.2 OH                                                                          ##STR187##                                               2  HOCH.sub.2 CH.sub.2 CH.sub.2 OH                                                                 ##STR188##                                               3  HO(CH.sub.2).sub.4OH                                                                            ##STR189##                                               4  HO(CH.sub.2).sub.6OH                                                                            ##STR190##                                               5  HOCH.sub.2(CH.sub.2).sub.8CH.sub.2 OH                                                           ##STR191##                                                   ##STR192##                                                                                     ##STR193##                                               7                                                                                 ##STR194##                                                                                     ##STR195##                                               8                                                                                 ##STR196##                                                                                     ##STR197##                                               9  HOC.sub.2 H.sub.4SC.sub.2 H.sub.4OH                                                             ##STR198##                                               10                                                                                ##STR199##                                                                                     ##STR200##                                               __________________________________________________________________________

EXAMPLE 3

A mixture consisting of 7.80 g of the dyestuff acid chloride of theformula ##STR201## (in the form of the chlorobenzene-moist material fromthe filter), 5.40 g of p-toluidine, 2.40 g of pyridine and 50 ml ofo-dichlorobenzene is stirred at a temperature of 110° for 6 hours. It isallowed to cool to 90° and the product is filtered off using a suctionfilter and washed with o-dichlorobenzene, then with methanol, then with1 N hydrochloric acid at about 60° and with water again until thefiltrate gives a neutral reaction. The product is then dried at 100°.

The dyestuff of the formula ##STR202## which is thus obtained isrecrystallised from 10 parts of dimethylformamide. A finely crystallinered powder is obtained.

If, with an otherwise identical procedure, equivalent amounts of theamines listed under I in the table which follows are used in place ofp-toluidine, the dyestuffs of column II, all of which dye polyesterfibres in brilliant red shades, are obtained.

    __________________________________________________________________________    I                   II                                                        Amines              Dyestuffs                                                 __________________________________________________________________________       ##STR203##                                                                                      ##STR204##                                               2                                                                                ##STR205##                                                                                      ##STR206##                                               3                                                                                ##STR207##                                                                                      ##STR208##                                               4                                                                                ##STR209##                                                                                      ##STR210##                                               5                                                                                ##STR211##                                                                                      ##STR212##                                               6                                                                                ##STR213##                                                                                      ##STR214##                                               7                                                                                ##STR215##                                                                                      ##STR216##                                               8                                                                                ##STR217##                                                                                      ##STR218##                                               9                                                                                ##STR219##                                                                                      ##STR220##                                               10                                                                               ##STR221##                                                                                      ##STR222##                                               11                                                                               ##STR223##                                                                                      ##STR224##                                               12                                                                               ##STR225##                                                                                      ##STR226##                                               13                                                                               ##STR227##                                                                                      ##STR228##                                               14                                                                               ##STR229##                                                                                      ##STR230##                                               15                                                                               ##STR231##                                                                                      ##STR232##                                               16                                                                               ##STR233##                                                                                      ##STR234##                                               17                                                                               ##STR235##                                                                                      ##STR236##                                               18                                                                               ##STR237##                                                                                      ##STR238##                                               19                                                                               ##STR239##                                                                                      ##STR240##                                               20                                                                               ##STR241##                                                                                      ##STR242##                                               21                                                                               ##STR243##                                                                                      ##STR244##                                               22                                                                               ##STR245##                                                                                      ##STR246##                                               23                                                                               ##STR247##                                                                                      ##STR248##                                               24                                                                               ##STR249##                                                                                      ##STR250##                                               25                                                                               ##STR251##                                                                                      ##STR252##                                               26                                                                               ##STR253##                                                                                      ##STR254##                                               27                                                                               ##STR255##                                                                                      ##STR256##                                               28                                                                              H.sub.2 NCH.sub.2 CH.sub.2 OH                                                                    ##STR257##                                               29                                                                               ##STR258##                                                                                      ##STR259##                                               30                                                                               ##STR260##                                                                                      ##STR261##                                               31                                                                               ##STR262##                                                                                      ##STR263##                                               32                                                                               ##STR264##                                                                                      ##STR265##                                               33                                                                               ##STR266##                                                                                      ##STR267##                                               34                                                                               ##STR268##                                                                                      ##STR269##                                               35                                                                               ##STR270##                                                                                      ##STR271##                                               36                                                                               ##STR272##                                                                                      ##STR273##                                               37                                                                               ##STR274##                                                                                      ##STR275##                                               38                                                                               ##STR276##                                                                                      ##STR277##                                               39                                                                               ##STR278##                                                                                      ##STR279##                                               40                                                                               ##STR280##                                                                                      ##STR281##                                               41                                                                               ##STR282##                                                                                      ##STR283##                                               42                                                                               ##STR284##                                                                                      ##STR285##                                               43                                                                               ##STR286##                                                                                      ##STR287##                                               44                                                                               ##STR288##                                                                                      ##STR289##                                               45                                                                               ##STR290##                                                                                      ##STR291##                                               __________________________________________________________________________

EXAMPLE 4

A mixture of 18.9 ml of phosphorus oxychloride and 18 ml ofchlorobenzene is allowed to run dropwise, in the course of about 30minutes, at a temperature of 100°, into a mixture consisting of 17.5 gof 4-bromo-naphthostyryl-5-carboxylic acid, 10.5 g ofbenzthiazolyl-acetonitrile and 90 ml of chlorobenzene and the resultingmixture is then stirred at the same temperature for a further 3 hours.It is then diluted with 15 ml of chlorobenzene and allowed to cool toroom temperature and the acid chloride of the formula ##STR292## whichhas formed is isolated by filtration and then washed several times withsmall amounts of chlorobenzene. The acid chloride is used direct in thisform for the preparation of the dyestuff.

If, with an otherwise identical procedure, equivalent amounts of4-chloro-naphthostyryl-5-carboxylic acid are used in place ofbromo-naphthostyryl-carboxylic acid, the acid chloride of the formula##STR293## is obtained.

If, using the same procedure, equivalent amounts of thenaphthostyryl-carboxylic acids listed under I in the table which followsand of the heterocyclic compounds listed under II are used, the acidchlorides of column III are obtained.

                                      TABLE                                       __________________________________________________________________________       I       II               III                                                  Naphthostyryl-                                                             No.                                                                              carboxylic acids                                                                      Heterocyclic compounds                                                                         Acid chlorides                                    __________________________________________________________________________        ##STR294##                                                                            ##STR295##                                                                                     ##STR296##                                       2  "                                                                                      ##STR297##                                                                                     ##STR298##                                       3  "                                                                                      ##STR299##                                                                                     ##STR300##                                       4  "                                                                                      ##STR301##                                                                                     ##STR302##                                       5  "                                                                                      ##STR303##                                                                                     ##STR304##                                       6                                                                                 ##STR305##                                                                            ##STR306##                                                                                     ##STR307##                                       7  "                                                                                      ##STR308##                                                                                     ##STR309##                                       8  "                                                                                      ##STR310##                                                                                     ##STR311##                                       9  "                                                                                      ##STR312##                                                                                     ##STR313##                                       10 "                                                                                      ##STR314##                                                                                     ##STR315##                                       __________________________________________________________________________

EXAMPLE 5

A mixture consisting of 9.3 g of the acid chloride of the formula##STR316## 5.4 g of p-toluidine, 2.4 g of pyridine and 30 ml ofchlorobenzene is stirred at a temperature of 110° for 6 hours. Themixture is allowed to cool to 90° and the dyestuff which has formed isisolated by filtration and washed several times with chlorobenzene, thenwith methanol, then with hot 1% strength hydrochloric acid and finallywith water until the filtrate gives a neutral reaction. The dyestuff isdried in vacuo at 100° and subsequently purified by recrystallisationfrom 10 parts of dimethylformamide. The dyestuff of the formula##STR317## is obtained in the form of a red powder which dissolves inorganic solvents to give a red solution.

In order to sulphonate the dyestuff, 1 part of dyestuff is introducedinto 10 parts of sulphuric acid monohydrate and the mixture is stirredat a temperature of 20° to 25° for 24 hours, after which the sulphonateddyestuff is isolated in the manner described in Example h) by pouringthe mixture onto ice; the dyestuff is then converted into the sodiumsalt.

When applied from a weakly acid aqueous solution, the dyestuff dyespolyamide fabric brilliant red. The resulting dyeings possess goodfastness properties.

If, with an otherwise identical procedure, equivalent amounts of theacid chlorides listed in the table which follows are used in place ofthe acid chloride mentioned initially and equivalent amounts of thecorresponding amines are used in place of p-toluidine, dyestuffs areobtained which, after sulphonation, dye polyamide fabric red. Thedyeings show good fastness properties.

                                      TABLE                                       __________________________________________________________________________     ##STR318##                                                                   No.                                                                              Amine        Dyestuff                                                      __________________________________________________________________________        ##STR319##                                                                                 ##STR320##                                                   2                                                                                 ##STR321##                                                                                 ##STR322##                                                   3                                                                                 ##STR323##                                                                                 ##STR324##                                                   4                                                                                 ##STR325##                                                                                 ##STR326##                                                   5                                                                                 ##STR327##                                                                                 ##STR328##                                                   6                                                                                 ##STR329##                                                                                 ##STR330##                                                   7                                                                                 ##STR331##                                                                                 ##STR332##                                                   8                                                                                 ##STR333##                                                                                 ##STR334##                                                   9                                                                                 ##STR335##                                                                                 ##STR336##                                                   10                                                                                ##STR337##                                                                                 ##STR338##                                                   11                                                                                ##STR339##                                                                                 ##STR340##                                                   12                                                                                ##STR341##                                                                                 ##STR342##                                                   13                                                                                ##STR343##                                                                                 ##STR344##                                                   14                                                                                ##STR345##                                                                                 ##STR346##                                                   15                                                                                ##STR347##                                                                                 ##STR348##                                                   16                                                                                ##STR349##                                                                                 ##STR350##                                                   17                                                                                ##STR351##                                                                                 ##STR352##                                                   18                                                                                ##STR353##                                                                                 ##STR354##                                                   19                                                                                ##STR355##                                                                                 ##STR356##                                                   20                                                                                ##STR357##                                                                                 ##STR358##                                                   21                                                                                ##STR359##                                                                                 ##STR360##                                                   22                                                                                ##STR361##                                                                                 ##STR362##                                                   23                                                                                ##STR363##                                                                                 ##STR364##                                                   24                                                                                ##STR365##                                                                                 ##STR366##                                                   25                                                                                ##STR367##                                                                                 ##STR368##                                                   26                                                                                ##STR369##                                                                                 ##STR370##                                                   27                                                                                ##STR371##                                                                                 ##STR372##                                                   28                                                                                ##STR373##                                                                                 ##STR374##                                                   29                                                                                ##STR375##                                                                                 ##STR376##                                                   30                                                                                ##STR377##                                                                                 ##STR378##                                                   31                                                                                ##STR379##                                                                                 ##STR380##                                                   32                                                                                ##STR381##                                                                                 ##STR382##                                                   33                                                                                ##STR383##                                                                                 ##STR384##                                                   34                                                                                ##STR385##                                                                                 ##STR386##                                                   35                                                                                ##STR387##                                                                                 ##STR388##                                                   36                                                                                ##STR389##                                                                                 ##STR390##                                                   37                                                                                ##STR391##                                                                                 ##STR392##                                                   38                                                                                ##STR393##                                                                                 ##STR394##                                                   39                                                                                ##STR395##                                                                                 ##STR396##                                                   40                                                                                ##STR397##                                                                                 ##STR398##                                                   41                                                                                ##STR399##                                                                                 ##STR400##                                                   42                                                                                ##STR401##                                                                                 ##STR402##                                                   43                                                                                ##STR403##                                                                                 ##STR404##                                                   44                                                                                ##STR405##                                                                                 ##STR406##                                                   45                                                                                ##STR407##                                                                                 ##STR408##                                                   46                                                                                ##STR409##                                                                                 ##STR410##                                                   47                                                                                ##STR411##                                                                                 ##STR412##                                                   48                                                                                ##STR413##                                                                                 ##STR414##                                                   49                                                                                ##STR415##                                                                                 ##STR416##                                                   50                                                                                ##STR417##                                                                                 ##STR418##                                                   51                                                                                ##STR419##                                                                                 ##STR420##                                                   52                                                                                ##STR421##                                                                                 ##STR422##                                                   53                                                                                ##STR423##                                                                                 ##STR424##                                                   54                                                                                ##STR425##                                                                                 ##STR426##                                                   55                                                                                ##STR427##                                                                                 ##STR428##                                                   56                                                                                ##STR429##                                                                                 ##STR430##                                                   57                                                                                ##STR431##                                                                                 ##STR432##                                                   58                                                                                ##STR433##                                                                                 ##STR434##                                                   59                                                                                ##STR435##                                                                                 ##STR436##                                                   60                                                                                ##STR437##                                                                                 ##STR438##                                                   __________________________________________________________________________

EXAMPLE 6

4 g of the compound of the formula ##STR439## are introduced into 40 gof sulphuric acid monohydrate, whilst stirring, and the mixture is thenstirred at room temperature for 24 hours, after which it is poured intoa mixture of 75 g of ice and 25 ml of a 25% strength solution of sodiumchloride. The precipitate which has formed is filtered off and thensuspended in 50 ml of water. The pH value of the mixture is corrected to7.0 by adding 1 N sodium hydroxide solution and the mixture is thenwarmed to 90°, 10 g of sodium chloride are introduced and thetemperature is maintained for 10 minutes, after which the mixture isallowed to cool. The sodium salt of the dyestuff formed is isolated at atemperature of 55° by filtration and is then dried in vacuo at 70°. Thedyestuff which is thus obtained is a red powder which dissolves in waterto give a red solution.

When applied from a weakly acid bath to polyamide fabric it gives abrilliant scarlet dyeing with good fastness to wet processing and goodfastness to light.

If the dyestuffs of the above table are used in place of the compoundmentioned above and these dyestuffs are sulphonated with sulphuric acidmonohydrate or oleum, which has a SO₃ content in the range up to 10%,and in the temperature range of 10° to 40°, so that in each case one toat most two sulpho groups are introduced, dyestuffs which dye polyamidefabric (abbreviated as PA) red and have similar good properties, areobtained.

If, in place of the compounds of the above table, the dyestuffs listedin the table which follows are so sulphonated, in the manner describedabove, that the acid dyestuffs formed contain one to at most two sulphogroups, dyestuffs which have similar properties on polyamide fabric areagain obtained.

    ______________________________________                                                                     Shade                                            Dyestuffs                    on PA                                            ______________________________________                                              ##STR440##                 red                                          2                                                                                   ##STR441##                 red                                          3                                                                                   ##STR442##                 red                                          4                                                                                   ##STR443##                 red                                          5                                                                                   ##STR444##                 red                                          6                                                                                   ##STR445##                 red                                          7                                                                                   ##STR446##                 red                                          8                                                                                   ##STR447##                 red                                          9                                                                                   ##STR448##                 red                                          10                                                                                  ##STR449##                 red                                          11                                                                                  ##STR450##                 red                                          12                                                                                  ##STR451##                 red                                          13                                                                                  ##STR452##                 red                                          14                                                                                  ##STR453##                 red                                          15                                                                                  ##STR454##                 red                                          16                                                                                  ##STR455##                 red                                          17                                                                                  ##STR456##                 red                                          18                                                                                  ##STR457##                 red                                          19                                                                                  ##STR458##                 red                                          20                                                                                  ##STR459##                 red                                          21                                                                                  ##STR460##                 red                                          22                                                                                  ##STR461##                 red                                          23                                                                                  ##STR462##                 red                                          24                                                                                  ##STR463##                 red                                          25                                                                                  ##STR464##                 red                                          26                                                                                  ##STR465##                 red                                          27                                                                                  ##STR466##                 red                                          28                                                                                  ##STR467##                 red                                          29                                                                                  ##STR468##                 red                                          30                                                                                  ##STR469##                 red                                          31                                                                                  ##STR470##                 red                                          32                                                                                  ##STR471##                 red                                          33                                                                                  ##STR472##                 red                                          34                                                                                  ##STR473##                 red                                          35                                                                                  ##STR474##                 red                                          36                                                                                  ##STR475##                 red                                          37                                                                                  ##STR476##                 red                                      

EXAMPLE 7

2 g of the dyestuff obtained according to Example 1 are dispersed in4,000 g of water. 12 g of the sodium salt of o-phenylphenol, as aswelling agent, and 12 g of diammonium phosphate are added to thisdispersion and 100 g of a yarn made of polyethylene glycol terephthalateare dyed for 11/2 hours at 95° to 98°. The dyeing is rinsed andafter-treated with aqueous sodium hydroxide solution and a dispersingagent.

This gives a bluish-tinged red dyeing which is fast to washing, lightand sublimation.

If, in the above example, the 100 g of polyethylene glycol terephthalateyarn are replaced by 100 g of cellulose triacetate fabric, dyeing iscarried out under the indicated conditions and the dyeing is then rinsedwith water, a bluish-tinged red dyeing which has very good fastness towashing and sublimation is obtained.

EXAMPLE 8

2 g of the dyestuff obtained according to Example 1 are finely suspendedin 2,000 g of water which contains 4 g of oleylpolyglycol ether, in apressure-dyeing machine. The pH value of the dye bath is adjusted to 4to 5 with acetic acid.

100 g of a fabric made of polyethylene glycol terephthalate are nowintroduced at 50°, the bath is heated to 140° in the course of 30minutes and dyeing is carried out for 50 minutes at this temperature.The dyeing is then rinsed with water, soaped and dried. When theseconditions are maintained, a bluish-tinged red dyeing which is fast towashing, perspiration, light and sublimation is obtained.

The dyestuffs described in the other examples give dyeings of equalquality by this process.

If, in the above example, the 100 g of polyethylene glycol terephthalateyarn are replaced by 100 g of cellulose triacetate yarn, dyeing iscarried out under the indicated conditions and the dyeing is then rinsedwith water, a bluish-tinged red dyeing which has very good fastness tolight and sublimation is obtained.

EXAMPLE 9

Polyethylene glycol terephthalate fabric is impregnated, on a padder, at40° with a liquor of the following composition: 20 g of the dyestuffobtained according to Example 1, finely dispersed in 7.5 g of sodiumalginate, 20 g of triethanolamine, 20 g of octylphenolpolyglycol etherand 900 g of water.

The fabric, which is squeezed off to about 100%, is dried at 100° andthen set for 30 seconds at a temperature of 210°. The dyed goods arerinsed with water, soaped and dried. Under these conditions abluish-tinged red dyeing which is fast to washing, rubbing, light andsublimation is obtained.

The dyestuffs described in the other examples give dyeings of equalquality by this process.

EXAMPLE 10

100 g of "Banlon"® tricot (a polyamide fabric) are introduced at 40°into a dye bath which contains 1 g of the dyestuff obtained according toExample 7 and 3 ml of 85% strength formic acid in 5,000 ml of water.Whilst agitating well, the bath is heated to the boil in the course of30 minutes and dyeing is carried out for one hour at the boil. The dyedgoods are then carefully rinsed and dried. A clear, brilliant, scarletdyeing of good tinctorial strength is obtained.

EXAMPLE 11

100 g of wool, which has been well pre-wetted, are introduced at 50°into a dye bath which contains 1 g of the dyestuff obtained according toExample 7, 5 g of sodium sulphate and 3 ml of 40% strength acetic acidin 5,000 ml of water, the bath is heated to the boil in the course of 15minutes and dyeing is carried out for one hour at the boil. A clear,brilliant and fluorescent scarlet wool dyeing is obtained.

What is claimed is:
 1. A naphtholactam dyestuff of the formula##STR477## wherein R is hydrogen, alkyl of 1-8 carbons, hydroxyalkyl of2-3 carbons, alkoxyalkyl of 3-8 carbons, β-chloroethyl, β-cyanoethyl,alkoxycarbonylethyl wherein the alkoxy moiety thereof has 1-4 carbons,carbamoylethyl, N-alkylcarbamoylethyl wherein the alkyl moiety thereofhas 1-4 carbon atoms, N,N-dialkylcarbamoylethyl wherein each alkylmoiety thereof has 1-4 carbon atoms, cyclohexyl, benzyl, phenethyl,phenyl, or alkenyl of 1-5 carbon atoms; Y is --CN, --COCl, --CO--Q' or--COOR₁ ; X is --COOH, --COO.sup.⊖ cation.sup.⊕, --CN, --COOR₁, or --SO₂T; A is ##STR478## wherein the ring B is unsubstituted ormono-substituted by halo, lower alkyl, lower alkoxy, hydroxy, cyano,vinyl, nitro, lower alkylamino, dialkylamino, phenylamino N-phenyl-N-alkylamino, phenyl or phenoxy;Z is C₁ -C₄ alkyl, C₁ -C₄ alkoxy, Cl,Br, NO₂, phenylsulfonyl, C₁ -C₄ alkyl --S--, C₁ -C₄ alkylsulfonyl,cyano, --CONH₂, --CONH(C₁ -C₄ alkyl), CON(C₄ alkyl)₂ ; n is 0, 1 or 2;R₁ and R₁ ' are independently C₁ -C₁₈ alkyl which is unsubstituted orsubstituted by C₁ -C₄ alkoxy, hydroxy, chloro, bromo, cyano, carboxy,carb-C₁ -C₄ -alkoxy, sulfo, carboxamido or acetoxy; cyclopentyl;methylcyclohexy; trimethylcyclohexyl; cyclohexyl; phenyl, benzyl orphenethyl which are unsubstituted or monosubstituted by C₁ -C₄ -alkyl,lower alkoxy or halo; --CH₂ CH₂ SCH₂ CH₂ OH; C₂ -C₅ alkenyl; or##STR479## Q' is NHR₁ ' or NR₁ ', R₂ ^(') wherein R₂ ' has the samemeaning as R₁ ' as defined above; T is C₁ -C₈ alkyl, C₂ -C₈ alkenyl orC₆ -C₉ phenyl; and M is hydrogen or a cation.
 2. A dyestuff according toclaim 1, wherein X is CN.
 3. A naphtholactam dyestuff of the formula##STR480## wherein R is H or C₁ -C₅ alkyl,Z is H, Cl or Br, Y is CN,COCI, COQ' or COOR₁ ',where Q' is as defined in claim 1, R₁ ^(') isC₁₋₁₈ alkyl, C₁₋₁₈ hydroxyalkyl, --CH₂ CH₂ SCH₂ CH₂ OH; C₂₋₅ alkenyl,C₆₋₉ cycloakyl, phenyl, benzyl or phenethyl or ##STR481## and M ishydrogen or a cation.
 4. A dyestuff according to claim 1, of the formula##STR482##
 5. A dyestuff according to claim 3, of the formula ##STR483##6. A dyestuff according to claim 3, of the formula ##STR484##